Anthraquinone dyes

ABSTRACT

1,4-DIAMINOANTHRAQUINONES BEARING IN POSITION 2 A 1,2,4OXADIAZOLE GROUP WHICH IS SUBSTITUTED IN POSITION 3 BY AN AROMATIC OR ALIPHATIC RADICAL. These anthraquinone derivatives are valuable blue disperse dyes for use in dyeing and printing synthetic textile materials.

United States Patent Patsch et al. 51 June 20, 1972 [54] ANTHRAQUINONE DYES [72] Inventors: Manfred Patsch, Ludwigshafen; Heinz [56] References Cited Ellingsield, Frankenthal, both of Gennany UNITED STATES PATENTS [73] Assignee: Badische Anilin- & Soda-Fabrik Aktien- 70 6 w t l 260 3 7 5 g i Ludwigshafen Gap 3,2 ,030 8/19 6 eldlnger e a O many Primary Examiner-Alex Mazel [22] Filed: March 17, 1970 Assistant Examiner-R. V. Rush [21 1 pp Nod 20,405 3;trneyJ0hnst0n, Root, 0 Keeffe, Ketl, Thompson & Shur- [30] Foreign Application Priority Data [57] ABSTRACT March 20, 1969 Germany ..P l9 14 207.5 l,4-diaminoanthraquinones bearing in position 2 a 1,2,4-ox- Sept. 30, 1969 Germany ..P 19 49 295.6 adiazole group which is substituted in position 3 by an any matic or aliphatic radical. These anthraquinone derivatives [52] US. Cl ..260/307.5, 260/37 N, 260/40 R, are l bl bl di e d e for use in dyeing and printing 260/2471, 260/247-5 B synthetic textile materials. [5 l 1 Int. Cl. ..C07d 85/52 [58] Field of Search ..260/307, 247.1, 247.5 B 5 Claims, No Drawings ANTHRAQUINONE DYES (llIz-CHz-Cl, IIaoHaoHa-00Ha The novel dyes are of the formula: 0i a-(ma0ira0ua-01, -Cl-IzGlI2-COOOH2 0 Ha H 20 CHPOH2-OCHr-CH2 5 Q1 Q of special commercial interest are the blue dyes of the formula:

,dHa (EH3 $113 0 N112 X stands for a direct link or a bridging member comprising H O--, S or SO,--, X stands for a direct link or a 3 L bridging member comprising O, S or SO,, Z where R Stand for the radlcal stands for the radical H, ---CH;,, OH, Cl, Br, NO CH CH3 CH3 CH n stands for zero 2 or 3. i

a CH CH o Suitable radicals of the formula A-X-(CH,),,,-X'- CH2 Q 2 Q (CH -Z are for example: 0 CH3 The novel dyes maybe prdducedfor rarriple, by reacting H3O CH: a anthraquinone carboxylic acid chlorides of the formula:

where 2 stands for the aforementioned radical Y or for a nitro CH OH IV --0 2 -OCH,CH2CH o- H O a 2 Q or the correspondmg hydrochlondes, preferably in solvent or diluent and at a temperature of from 20 to 200 C., preferably from to 180 C., and where an anthraquinone derivative of formula Ill is used in which the radical Z is a nitro group the 1 a dye is completed by reducing or substituting the nitro group. LH2CH S- ,OH2-CHbO2- 2* Q 2 Q In formula IV above, D stands for the aforementioned group Where, instead. of the free carboxylic acid amidoximes of the formula N, there are used the corresponding hydrochlorides, the reaction of the compounds of formula III is carried out in the presence of a basic agent.

Suitable solvents or diluents for use in the reaction of the compounds Ill and IV are, for example, benzene, nitrobenzene, toluene, dichlorobenzene, chlorobenzene and dimethyl formamide. Suitable basifying agents are, for example, tertiary amines, such as triethylamine, tripropylamine, ethyl diisopropylamine, pyridine or potassium carbonate. The starting materials Ill and IV are conveniently used in stoichiometric amounts.

Anthraquinone derivatives containing nitro groups are, following the reaction with the compounds of formula IV, reduced or reacted with amines by usual methods in order to convert the nitro group to an amino group or to substituted amino group. For example, reduction may be carried out in solvents, such as dimethyl'formamide, N-methyl pyrrolidone, dichlorobenzene, glycol ethers or water, at temperatures ranging from 20 to 100 C. and beneficially from 30 to 60 C., with reducing agents such as sodium sulfide, hydrogen sulfide, sodium dithionite or hydrazine. Reactions with amines may be carried out, for example, in the solvents listed immediately above at temperatures ranging from 100 to 170 C.

The novel dyes are valuable disperse dyes for use in dyeing and printing synthetic textile materials such as fibrous materials made from polyester or polyamide fibers. The dyeings and printings thus obtained are characterized by good fastness to light and to cracking and by good thermal fastness properties. The novel dyes are also useful as pigment dyes and are suitable, for example, for the mass coloration of thermoplastic synthetic resins as also for the dope-dyeing of polyesters and polyamides.

The textile materials are dyed and printed with the novel dyes by the usual methods. Dyeing is carried out with dyebaths which conveniently contain the dyes in dispersion. Using such dyebaths, dyeing is carried out at temperatures between 95 and 100 C. at ambient pressure, or at temperatures above 100 C. by the high temperature process or the thermosol process. If it is desired to produce strong colorations at temperatures near 100 C., is is convenient to add a carrier. For printing polyester and polyamide fabrics use is made of printing pastes containing the said dyes in finely divided form together with the usual thickening agents and printing auxiliaries. It is convenient to add carriers to the printing pastes also. Very good results are also obtained when mixtures of the novel dyes are used.

In the following Examples, the parts are by weight.

EXAMPLE 1 16.6 parts of 1-amino-4-nitroanthraquinone-Z-carboxylic acid chloride in 150 parts of nitrobenzene and 1 part of triethylamine are heated with 6.8 parts of benzamidoxime at 15 C. for 2 hours. The mixture is allowed to cool and is then filtered. The solid residue is suspended in a solution of 18 parts of sodium sulfide (60%., flaked) in 300 parts of water and 4 parts of n-butyl, alcohol. After 2 hours at 80 C. the precipitate is filtered off and dried in vacuo at 50 C.

Yield: 15 parts of the dye of the following formula (melting point 294 to 296 C.

EXAMPLE 2 16.6 parts of l-amino-4-nitroanthraquinone-Z-carboxylic acid chloride and 8.2 parts of 2,5-dimethylbenzarnidoxime are heated in 150 parts of nitrobenzene and 1 part of triethylamine for 2 hours at 150 C. The precipitate is filtered ofi and dissolved in 130 partsof N-methyl pyrrolidone and parts of tripropylamine. Hydrogen sulfide is then passed through the solution for 3 hours at 30 to 40 C. The mixture is cooled and the precipitate filtered off and dried in vacuo at 50C. Yield: 16 parts of the dye of the following formula (melting point 300 to 302 C.):

NHz

EXAMPLE 3 16.6 parts of l-amino-4-nitroanthraquinone-2-carboxylic acid chloride and 8.2 parts of 2,4-dimethylbenzamidoxime are heated in 200 parts of glycol methyl ether and 2 parts of triethylamine for 3 hours at 150 C. After cooling, the precipitate is filtered off and dissolved in parts of N- methyl pyrrolidone and 75 parts of tripropylamine. Hydrogen sulfide is then passed through the solution for 2 hours at 30 to 40 C. The mixture is cooled and filtered, and i4 parts of the dye of the following formula (m.p. 282 to 285 C.) are isolated as solid residue:

Q O EH3 EXAMPLE 4 16.6 parts of 1-amin0-4-nitroanthraquinone-2-carboxylic acid chloride and 8.2 parts of 2,3-dimethylbenzamidoxime are heated in 80 parts of nitrobenzene and 1 part of tripropylamine for 4 hours at C. After cooling, the precipitate is filtered off, dried and heated in a solution of 18 parts of sodium sulfide (60% flaked) in 300 parts of water and 5 parts of n-butyl alcohol for 5 hours at 80 C. There are isolated 13 parts of the dye of the following formula (m.p. 280 to 283 C.):

40 C. There are isolated 14 parts of the dye of the following formula:

NHz

EXAMPLE 5 3,671,536 5 6 NH2 EXAMPLE 10 N @4311 Example 6 is repeated except that 3-(3-methoxyphenoxy) propionic acid amidoxime used as the compound of formula CH3 5 IV. There are thus isolated 15 parts of the dye of the formula:

l EXAMPLE 6 Q 16.6 parts of l-amino-4-nitroanthraquinone-Z-carboxylic 10 I acid chloride, ll.5 parts of 3-(2'-ethylmercapto)ethoxypropiouic acid amidoxime hydrochloride and 14.2 parts of ethyl diisopropylamine are heated together in 80 parts of nitrobenzene for 4 hours at 150 C. After cooling and effecting precipitation with 100 parts of methanol, the precipitate is EXAMPLE 1 1 filtered off and suspended in 200 parts of N-methyl pyrrolidone and l00 parts of tripropylamine. Hydrogen sulfide is passed through the suspension for 3 hours at 30 to 40 C. The mixture is cooled and filtered, and the solid residue is dried in 2 vacuo at 50 C. There are thus isolated 16.4 parts of the dye of O NH:

the following formula (m.p. 209 to 210 C): I

NHZ A h-CH2-CH2O-OHzCHzS or-cim C 2 2 0 2 2 S C2H5 I NH;

Example 6 is repeated except that 3.-(2-ethylsulfonethoxy) propionic acid amidoxime is used as the compound of formula 0 IV. There are thus obtained parts of the dye of the formula:

I A PLE12 EXAMPLE 7 EX M Example 6 is repeated except that 3-(2-n-butoxyethyl) Example 6 is repeated except that z-methym'ethylmemap' propionic acid amidoxime is used as the compound of formula to propionic acid amidoxime hydrochloride is used as the d 23 HS fthe d e of the formula; compound of formula IV. There are thus obtained 17 parts of 3 5 There are thus ob me pa 0 y the dye of the formula:

0 NH 011 I NH; N l 2 l a A T -OHQCHZOCHCH2-OC4H 1% CHCH2-SC2H6 N 0 40 Y Y 111E: I w iHz if Wat: W Vim. w

EXAMPLE 8 EXAMPLE 23 Example 6 is repeated except that 2-methyl-3-(2-hydr0x- Example 6 is repeated except that 3-[2-(2-propoxyethoxyethylmercapto) propionic acid amidoxime hydrochloride is y)ethoxy]propionic acid amidoxime is used as the compound used as the compound of formula IV. Yield: 16 parts of the of formula IV. There are thus obtained 25 parts of the dye of dye .of the formula: the formula:

0 NH! N V E LEELLM. PH?- fl A (I) NH2 N CH: EXAMPLE 14 v A E&H"CHZ S C H2CH2 OH Example 6 is repeated except that 3-(2-phenylethoxy) propionic acid amidoxime is used as the compound of formula 0 IV. There are thus obtained 21 parts of the dye of the formula:

0 l IHz V V h 0 I N N EXAMPLE9 A \{JQHPCEQ-O-CHFOHPQ Example 6 is repeated except that 3-morpholino propionic acid amidoxime hydrochloride is used as the compound of formula lV. Yield: 18 parts of the dye of the formula: Y

I lx-oaz-onz-N EXAMPLE 1s 16.6 parts of l-amino-4-nitroanthraquinone-Z-carboxylic acid chloride, 11.5 parts of 3-(2'-ethylniercapto)ethoxy Y propionic acid amidoxime hydrochloride and 14.2 parts of NH; ethyl diisopropylamine are heated in parts of nitrobenzene for 4 hours at 150 C. The mixture is allowed to cool and precipitation is effected with 100 parts of methanol. The precipitate is filtered off and heated together with 5 parts of 3- amino propanol in 80 parts of butyl glycol for 3 hours at 160 to 170 C. The mixture is allowed to cool and the precipitate is 5 filtered off. Yield: 18 parts of the dye of the formula:

0 NHz N 1 .9 EETPEZTQECEHE EXAMPLE 16 16.6 parts of l-amino-4-nitroanthraquinone-2-carboxylic acid chloride, 6.8 parts of benzamidoxime and 1 part of 20 triethylamine are heated in 150 parts of nitrobenzene for 2 hours at 150 C. The mixture is allowed to cool and the precipitate is filtered off and then heated with 5 parts of 3- methoxy propylamine in 80 parts of butyl glycol for 3 hours at 160 C. There are isolated 17 parts of the dye of the formula:

The following dyes are obtained by operating in a similar manner to that described in Example 15 and 16:

x lj I as red crystals having a melting point of 282285 C. The corresponding 1,4-di-aminoanthraquinone derivative is obtained by dissolving, for example, 10 parts of the l-amino-4- nitroanthraquinone derivative in 100 parts of N-methyl pyrrolidone and 20 parts of tripropylamine and passing hydrogen sulfide through the solution for 3 hours at to C. After cooling, the precipitate is filtered off and there are obtained 8 parts of 1,4-diaminoanthraquinone derivative, m.p. 281 C. The dye dyes polyester and polyamide fabrics in blue shades.

EXAMPLE 24 33.2 parts of 1-amino-4-nitroanthraquinone -2-carboxylic acid chloride are dissolved in 400 parts of dimethyl formamide. 13.8 parts of propionic acid amidoxime hydrochloride and 31.5 parts of tripropylamine are added and the mixture is heated for 2 hours at C. and for 5 hours at C. After cooling, the precipitate is filtered off, dissolved in 80 parts of N-methyl pyrrolidone and 10 parts of tripropylamine and reduced to the blue dye of the following formula by passing hydrogen sulfide through the solution at 70-80 C:

O NH:

l O--N Example Y R NH CH3 l8 NHC2H EXAMPLE 23 33.2 parts of l-amino-4-nitr0anthraquinone-2-carboxylic acid chloride are reacted with 12.2 parts of acetamidoxime hydrochloride and 28.4 parts of ethyl diisopropylamine in 400 parts of nitrobenzene by heating at 100 C. for 2 hours and then at C. for 4 hours. After cooling, the precipitate is filtered offand dried. There are thus obtained 28 parts of the compound of the formula:

23 parts of the dye are isolated; m.p. 273275 C.

EXAMPLE 25 33.2 parts of 1-amino-4-nitroanthraquinone-2-carboxylic acid chloride, 17.1 parts of fl-methoxypropionic acid amidoxime hydrochloride and 28.4 parts of ethyl diisopropylamine are dissolved in 500 parts of glycol dimethylether. The mix- 75 ture is heated for 2 hours at 60 -70 C. and is then heated under reflux for 7 hours. After cooling, the mixture is filtered, and the residue is dissolved in 100 parts of methyl glycol and 20 parts of triethylamine. Hydrogen sulfide is passed through the solution for 1 hour at 7080 C. There are isolated 26 parts ofthe dye of the following formula (m.p. 240-245 C.):

I NHz This dye dyes polyester and polyamide fabrics in blue shades.

EXAMPLE 26 EXAMPLE 27 33.2 parts of 1-amino-4-nitroanthraquinone-2-carboxylic acid chloride and 18.8 parts of phenylacetamidoxime hydrochloride are dissolved in 120 parts of nitrobenzene and 14 parts of ethyl diisopropylamine and stirred for 2 hours at 100 C. and for a further 3 hours at 150 C. The mixture is allowed to cool and is filtered. The isolated red crystals are dissolved in 100 parts of N-methyl pyrrolidone and parts of tripropylamine. Hydrogen sulfide is passed through the solution for 7 hours at 30 to 40 C. After cooling, 25 parts of the dye of the following formula are isolated (m.p. 258-259 C.):

NTFCHQ O NHz EXAMPLE 28 .lll EXAMPLE 29 Example 28 is repeated except that the 2-rnethyl-3-methoxypropionic acid amidoxime hydrochloride is replaced by a corresponding amount of 2-methyl-3-isoproppoxypropionic acid amidoxime hydrochloride. There are thus obtained 18 parts of the dye of the formula:

EXAMPLE 30 Example 28 0240 is repeated except that the 2-methyl-3- methoxypropionic acid amidoxime hydrochloride is replaced by a corresponding amount of 2-isobutoxypropionic acid amidoxime hydrochloride. There are thus obtained 15 parts of the dye of the formula:

0 NHz NE L.

EXAMPLE 31 Example 28 is repeated except that the 2-methyl-3-methoxypropionic acid amidoxime hydrochloride is replaced by a corresponding amount of B-dimethylaminopropionic acid amidoxime hydrochloride. There are thus obtained 15 parts of the dye of the formula:

CHrr H zh EXAMPLE 32 I i Q i: L I

EXAMPLE 33 I 33.2 parts of l-amino-4-nitroanthraquinone-2-carboxylic acid chloride, 17 parts of 4nitrobenzamidoxime and 1 part of tripropylamine are heated together in 300 parts of nitrobenzene for 3 hours at C. After cooling, the precipitate is filtered off and dissolved in 200 parts of N- methyl pyrrolidone. Hydrogen sulfide is then passed through A stands for the radical the solution to produce the dye of the following formula by reduction: (1 11a 5 Q 0111-, Jam-culr AHs (5H: H: i CH3 l CHCI IzCHz--, CH-CH2 or CH2--GH2OHzOHr X is a direct link or the bridging member O-, S or Yield: 30 parts. 2-,

X' is a direct link or the bridging member -O-, S or EXAMPLE 34 30, 16.6 parts of l-nitroanthraquinone-Z-carboxylic acid ig z g the radical CH3 chloride, 12 parts of 3-[2'-(2"-butoxyethoxy)ethoxylpro pionic acid amidoxime and 1 part of tripropylamine are H:

heated together in 120 parts of nitrobenzene-for 3 hours at 1 150 c. The mixture is allowed to cool and is filtered. The Q oc a, 2 5, 1 solid residue is dissolved in 100 parts of N-methyl pyrrolidone and hydrogen sulfide is passed through the solution for 3 hours 04H, O 0 CH3 (0113)" or at room temperature. There are then lsolated 14 parts of the dy ofthe formula: m M" m ls zero, 1 or 2 and 0 N Hz n is zero, 2 or 3, with the proviso that X and X are dlrect llnks C2H4'O'C2H40'C2Hr-OC4H when both 01 and n are zero and that X is a direct link when m ornis zero.

I O- 2. The dye of the formula:

acid chloride, 12 parts of B-triethoxypropionic acid amidox- M h f l ime and 1 part of tripropylamine are heated together in 120 The dye e parts of nitrobenzene for 3 hours at 150 C. The mixture is al- 40 0 I lowed to cool and is filtered. The precipitate is dissolved in l N -CH -O 100 parts of N-methyl pyrrolidone and hydrogen sulfide is passed through the solution for 3 hours at room temperature. OCH:

NHz 4 There are then isolated 13 parts of the dye of the formula:

I I Q We claim: I 1. An anthraquinone dye of the formula:

O NH2 seen:

Patent No. 3,671,536 Y Dated June 1972- Manfred Patsch Inventor(s) It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 1, line 11, the right-hand portion of the formula reading "-NNCH ,NNCH H should read -NHCH ,NHCH H 7-,

same column 1, lines 15, 24, 27, 40 and 49, after the first and last structure, each occurrence insert a comma; "line"'59,' after I the first and last structurefli nes 54,63, 65, 69, 71, 73 and 75, 1 column 2, lines 1, 2, 3, 4, 6, 9, 10 11, 12, 1s, 14, 15, 16 17, 34 38, 39 4O, 41, 42, 44 and line 68, column '11, after the last structure, column 12, lines 5', 9, 20 and 22, at the end'of each line' insert a comma. Column .1, lines 64 and' 65, the left- ,hand portion of the structure reading -CH -CH J should read -CH .CH I-N 0 Column 2, line 22, "of special commercial interest are the blue dyes of the formula" should appear in Roman type; line 31, "stand" should read stands line 49', after the last structure insert a period; line 69, after "in" insert a Column 5, lines 11 and 12, "ethylmercapto)ethoxypropionic acid amidoxime hydrochloride and" should appear in Roman type. Column 10, line 20 cancel "0240" Signed and sealed this 24th day of April 1973.

(SEAL) Attest:

EDWARD M.PLETCHER,JR. ROBERT GOTTSCHALK Attesting Officer 2 Commissioner of Patents O PC4050 (10-69) USCOMM-DC 60376-P69 U.S. GOVERNMENT PRINTING OFFICE: '56! O-IGG-SSL 

2. The dye of the formula:
 3. The dye of the formula:
 4. The dye of the formula:
 5. The dye of the formula: 